CN103323447B - The assay method of sulfur content in a kind of extreme pressure cutting fluid - Google Patents
The assay method of sulfur content in a kind of extreme pressure cutting fluid Download PDFInfo
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Abstract
The invention belongs to cutting fluid chemical composition analysis technical field of measurement and test, the assay method of sulfur content in a kind of extreme pressure cutting fluid is disclosed, adopt red fuming nitric acid (RFNA) and perchloric acid, make sample catapepsis, be converted into inorganic samples aqueous solution, under ICP inductive coupling plasma emission spectrograph condition of work, measure sulfur content in cutting fluid; Specifically comprise that experiment condition is determined, analyzing detecting method, determination of recovery rates; The present invention adopts nitric acid, perchloric acid clears up extreme pressure cutting fluid sample, makes it be converted into inorganic samples aqueous solution completely, under the ICP inductive coupling plasma emission spectrograph condition of work of the best, measures sulfur content in extreme pressure cutting fluid.Have easy to operate, reduce the use of chemical reagent, can meet the requirement of sulphur content determination in extreme pressure cutting fluid while meeting environmental requirement, measure sulfur content expense low, good stability, measurement result is accurate.
Description
[technical field]
The invention belongs to cutting fluid chemical composition analysis technical field of measurement and test, relate to test methods of sulphur contents in a kind of mensuration extreme pressure cutting fluid, refer more particularly to the ICP inductively coupled plasma atomic emission determination techniques of sulfur content in extreme pressure cutting fluid.
[technical background]
Extreme pressure cutting fluid refers to the cutting fluid adding active or nonactive extreme-pressure additive, and sulfur-bearing extreme pressure cutting fluid refers to the cutting fluid containing active or inactive sulfur adjuvant.When sulfur-bearing extreme pressure cutting fluid at high temperature cuts, there is chemical reaction in the interface of blade and section, form a kind of effective boundary lubricant film, prevent metal from contacting with the direct of metal, the wearing and tearing of minimizing cutter.Extreme pressure cutting fluid high lubricating effect containing active sulphur, the ability of restrain built-up edge and scale is strong, but sulfur-bearing cutting fluid can produce corrosion to non-ferrous metal, therefore, sulfur-bearing extreme pressure cutting fluid is generally applicable to comparatively difficult Cutting Process operation, for highly difficult tapping or thread turning processing.
Due to the difference of sulfur content in extreme pressure cutting fluid, its extreme pressure property has difference, the simplest sulfide mineral oil formula sulfur-bearing about 1%, can be used for the cutting operation technique of general difficulty processing, and for such as highly difficult tapping or thread turning processing, in extreme pressure cutting fluid, sulfur content can reach 5%, and measuring sulfur content in cutting fluid is also one of index of cutting fluid quality control.Therefore according to different machining workpieces and processing technology, select different extreme pressure cutting fluids, to reach best Process configuration, therefore, the content measuring sulphur in extreme pressure cutting fluid has a very important role to instructing Cutting Process.
In current existing mensuration cutting fluid, the assay method of sulfur content is little, and the method for sulphur mostly is the assay method measuring sulphur in petroleum products or adjuvant, as:
1) Jiang Gao, Qi Bangfeng, Zhang Huicheng etc., Study for Determination of Sulfur in Heave Petroleum Products by UltravioLet Fluorescene Method, adopt high-temperature gasification to generate sulphuric dioxide, sulphuric dioxide is subject to feature UV-irradiation, the ultraviolet principle of Absorption Characteristics measures sulfur content, employing be special chemiluminescence constant sulphur appliance.
2) Liu Wangjuan, Zhao Gaiping, the Determination of Trace Sulfur content assaying method research in oils, adopts micro-coulometric determination Determination of Trace Sulfur.
3) Wang Hong, husky Naruhito, Li Yong etc., inductively coupled plasma emission spectrography surveys sulphur in glass.
4) Bai Shengjun, Lin Jianrong, still mound, inductively coupled plasma emission spectrography measures the content of Sulfur content in Fuel Oil, adopts the sulphur in acid extractants partition method collection working sample.
The assay method of comprehensive above-mentioned sulphur, method 1), 2) be measure sulfur content in petroleum products, adopt ultraviolet fluorescence method and small-hole drilling all to need the conversion process of sulphur and sulphuric dioxide in sample, its conversion ratio affects by several factors, not too applicable to sulfur content in mensuration cutting fluid.Method 3) in be the sulphur measured in glass, sample preparation and cutting fluid sample preparation different.Method 4) the middle content measuring Sulfur content in Fuel Oil, adopt the sulphur in acid extractants partition method collection working sample, be difficult to the combined sulfur extracted in cutting fluid, cause measurement result on the low side.Therefore the method for said determination sulfur content can not meet the mensuration of sulfur content in extreme pressure cutting fluid, and in extreme pressure cutting fluid, analysis of sulfur content measures, and has become a problem demanding prompt solution in the control of extreme pressure cutting fluid performance index.
[summary of the invention]
For solving the problems of the technologies described above, the invention provides the assay method of sulfur content in a kind of extreme pressure cutting fluid, there is good stability, measurement result is accurate, easy to operate, reduce the use of chemical reagent, the requirement of sulphur content determination in extreme pressure cutting fluid can be met while meeting environmental requirement.
To achieve these goals, the present invention adopts following technical scheme:
An assay method for sulfur content in extreme pressure cutting fluid, adopts red fuming nitric acid (RFNA) to make sample catapepsis become aqueous solution with perchloric acid, is converted into inorganic samples aqueous solution, under inductive coupling plasma emission spectrograph ICP condition of work, measures sulfur content in cutting fluid; Its concrete steps are as follows:
1, the determination of experiment condition:
A. treatments of the sample acid: the reagent of employing is red fuming nitric acid (RFNA), perchloric acid, and the consumption of red fuming nitric acid (RFNA) and perchloric acid is respectively 20mL, 10mL;
B. inductive coupling plasma emission spectrograph ICP measures the condition of work of sulfur content: comprising: the setting of plasma emission power, peristaltic pump sample lifting capacity, analysis spectral line selection, cold gas, assisted gas, plasma (orifice) gas, quarter bend pipe core distance, the selection of integral time;
2, analyzing detecting method:
A. sample clear up process: take cutting fluid 0.2000g in 250mL beaker, add red fuming nitric acid (RFNA) 20mL, perchloric acid 10mL, sample is placed on hot digestion on middle temperature electric furnace, after treatments of the sample is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
B. the preparation of working curve: the cutting fluid 0.2000g6 part taking not sulfur-bearing is placed in the beaker of 6 250mL respectively, by the condition process of a step Specimen eliminating of step 2, after cooling, proceeds in the volumetric flask of 6 100mL.Drawing reagent is the different amount of the sulphur standard solution of 1.0mg/mL, and be placed in the volumetric flask of aforesaid 6 100mL respectively, be diluted with water to 100mL and carve, shake up, this group liquid is working curve liquid to be determined;
C. the determination of inductive coupling plasma emission spectrograph ICP condition of work:
Inductive coupling plasma emission spectrograph ICP condition of work and running parameter as follows: RF power:
1.1KW; Cooling gas flow: 20mL/min, assisted gas flow 0.5mL/min, plasma gas flow rate 38mL/min; Integral time 30s; Peristaltic pump sample lifting capacity 1.8mL, quarter bend pipe core distance is 5.0mm, analysis spectral line: 180.731nm;
D. sample tests: under selected instrument condition of work, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur element to be determined, instrument is according to sulfur content and the corresponding luminous intensity values drawing curve measured.Sulfur content in cutting fluid sample is measured with condition with working curve;
3, determination of recovery rates:
Take not sulfur-bearing cutting fluid 0.2000g each 3 parts in 3 250mL beakers, adding reagent 1mg/mL sulphur mark liquid measure is respectively 2.0mg, 4.0mg, 6.0mg, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution element sulphur in analyzing detecting method, measured value is respectively: 1.98mg, 4.01mg, 5.97mg, the recovery is respectively: 99.0%, 100.25%, 99.5%, illustrate that the method accuracy of measurement is higher, meet the requirement that in extreme pressure cutting fluid, sulfur content detects;
Take not sulfur-bearing cutting oil 0.2000g each 3 parts in 3 250mL beakers, adding reagent 1mg/mL sulphur mark liquid measure is respectively 2.0mg, 4.0mg, 6.0mg, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution element sulphur in analyzing detecting method, measured value is respectively: 1.96mg, 4.00mg, 5.98mg, the recovery is respectively: 98.0%, 100.0%, 99.7%, illustrate that the method accuracy of measurement is higher, meet the requirement that in extreme pressure cutting oil, sulfur content detects.
An assay method for sulfur content in extreme pressure cutting fluid, reagent is: red fuming nitric acid (RFNA); Perchloric acid; Not sulfur-bearing cutting fluid; Not sulfur-bearing cutting oil; Sulphur standard solution: 1.0mg/mL; Phosphorus standard solution: 1.0mg/mL; Boron standard solution: 1.0mg/mL.It is pure that described reagent is analysis: water used is distilled water;
The assay method of sulfur content in a kind of extreme pressure cutting fluid, exist owing to having active sulphur and inactive sulfur in extreme pressure cutting fluid, treatments of the sample acid is avoided using reductive acid as far as possible, because reductive acid can generate sulfuretted hydrogen colloidal sol in treatments of the sample process, produce hydrogen sulfide gas effusion in heating process, make measurement result on the low side.Described molten sample acid is: the reagent of employing is red fuming nitric acid (RFNA) and perchloric acid, and the consumption of red fuming nitric acid (RFNA) and perchloric acid is respectively 20mL, 10mL; Take four parts, 0.2000g extreme pressure cutting fluid sample in 4 250mL beakers in, add the acid of 10mL, 15mL, 20mL, 25mL red fuming nitric acid (RFNA) respectively, after adding perchloric acid 3mL, 5mL, 10ml, 15mL, hot digestion sample on middle temperature electric furnace, after treatments of the sample is complete, emit perchloric acid cigarette 5min, sulfur oxide generates sulfate radical.Very fast and the red fuming nitric acid (RFNA) acid of clearing up that to be addition be completely of Specimen eliminating for 20mL, 25mL and perchloric acid be two samples of 10mL, 15mL, when ICP peristaltic pump promotes sample solution, acid in sample liquid can affect the atomizing effect of sample introduction speed and atomizer, select the acid treatment sample of lower appropriate amount as far as possible, the addition selecting red fuming nitric acid (RFNA) acid is 20mL, perchloric acid addition is 10mL;
The assay method of sulfur content in a kind of extreme pressure cutting fluid, described ICP radio-frequency generator RF power is determined: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, be settled to 100mL scale with water, shake up, measure the luminous intensity values of sulphur; Regulate different RF watt levels to test, the increase of RF power makes line strength strengthen, but background increase simultaneously is faster, and therefore signal-to-background ratio increases with RF power and declines.Test display RF power is conducive to obtaining large signal-to-background ratio and Detection capability time low, but matrix effect is heavier; RF adopts high-powerly can alleviate matrix effect, but signal-to-background ratio and detection limit impaired, and easily burn out quarter bend when RF power is excessive.Test selects RF power to be 1.1KW;
The assay method of sulfur content in a kind of extreme pressure cutting fluid, described ICP is gases used is high-purity argon gas, the determination of argon flow amount: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, be settled to 100mL scale with water, shake up, measure the light intensity value of sulphur, regulate plasma (orifice) gas, cold gas and assisted gas flow, measure the light intensity value of sulphur.Test selected plasma gas flow rate 38L/min, cold gas 20L/min and assisted gas flow 0.5L/min;
An assay method for sulfur content in extreme pressure cutting fluid, the determination of described quarter bend pipe core distance: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, be settled to 100mL scale, shake up with water, measures the light intensity value of sulphur.Regulate the diverse location of quarter bend, measure the light intensity value of sulphur, torch tube hub pipe suitably should be increased to about 5.0mm place with the distance on edge under coil, and the absorbance of mensuration sulphur is maximum.Test determines that quarter bend pipe core distance is for 5.0mm;
The assay method of sulfur content in a kind of extreme pressure cutting fluid, the selection of described analysis spectral line wavelength: because the analysis spectral line of the sulphur of instrument recommendation is: 180.731nm, 182.624nm and 182.034nm, belong to ultraviolet spectral line, more suitable to sulfur content in extreme pressure cutting fluid or cutting oil, but in extreme pressure cutting fluid or extreme pressure cutting oil except sulfur-containing additive, also may there is phosphorous and adjuvant that is boracic, the analysis spectral line of phosphorus and boron is all positioned at ultraviolet region substantially, interference may be caused to the analysis spectral line of sulphur, the recommendation spectral line of phosphorus has: 213.618nm, 178.283nm, 253.561nm, 214.914nm, the recommendation spectral line of boron has: 249.677nm, 208.956nm, 208.890nm, 182.641nm, 249.772nm, by carrying out length scanning to the mixed sample containing phosphorus, boron and sulphur, only have the 182.624nm of the 182.641nm of boron to sulphur to have spectral line interference, test selects 180.731nm to be the analysis spectral line of sulphur,
The assay method of sulfur content in a kind of extreme pressure cutting fluid, the elimination of described Matrix effects, due in extreme pressure cutting fluid except there is extreme-pressure additive, also other adjuvant various can be contained, in order to working sample and typical curve match, not sulfur-bearing cutting fluid bottoming is selected in test, adds the sulphur mark liquid of corresponding different content, be mixed with standard working curve, in order to eliminate the interference that matrix brings.
Owing to have employed technique scheme, the present invention has following beneficial effect:
1) assay method of sulfur content in a kind of extreme pressure cutting fluid of the present invention, be clear up sample by employing red fuming nitric acid (RFNA), perchloric acid and convert it into sulfate, and measure sulfur content by application " ICP inductively coupled plasma emission spectrography ", its measurement result can be made more quick and precisely, and stable performance, reliable and practical.
2) assay method of sulfur content in a kind of extreme pressure cutting fluid of the present invention, the bad phenomenon such as the pipe core blocking that in ICP device, on quarter bend wall, organic carbon causes can be avoided to occur, that is, " special sampling device " expense (about 300,000 yuan) adopted needed for ICP inductively coupled plasma atomic emission organism mensuration can be saved.
The present invention adopts nitric acid, perchloric acid clears up extreme pressure cutting fluid sample, makes it be converted into inorganic samples aqueous solution completely, under the ICP inductive coupling plasma emission spectrograph condition of work of the best, measures sulfur content in extreme pressure cutting fluid.Have good stability, measurement result is accurate, easy to operate, reduces the use of chemical reagent, can meet the requirement of sulphur content determination in extreme pressure cutting fluid while meeting environmental requirement.
[embodiment]
The object of the assay method of sulfur content in open a kind of extreme pressure cutting fluid of the present invention, be intended to protect all changes and improvements in the scope of the invention, embodiment is below not limitation of the invention.The present invention can be explained in more detail by embodiment below:
The assay method of sulfur content in extreme pressure cutting fluid: adopt ICP inductively coupled plasma emission spectrography to measure a sulfur content in extreme pressure cutting fluid, specifically comprises that experiment condition is determined, analyzing detecting method, determination of recovery rates; Described extreme pressure cutting fluid, comprising: water base extreme pressure cutting fluid and oil base extreme pressure cutting fluid, be referred to as " extreme pressure cutting fluid ".
Reagent is: red fuming nitric acid (RFNA); Perchloric acid; Not sulfur-bearing cutting fluid; Not sulfur-bearing cutting oil; Sulphur standard solution:
1.0mg/mL; Phosphorus standard solution: 1.0mg/mL; Boron standard solution: 1.0mg/mL.It is pure that described reagent is analysis; Water used is distilled water;
It is ICP inductive coupling plasma emission spectrograph with instrument; Its step is as follows:
The determination of 1 experiment condition:
1.1 sample digestion acid: exist owing to having active sulphur and inactive sulfur in extreme pressure cutting fluid, treatments of the sample acid is avoided using reductive acid as far as possible, due to the existence of reductive acid, sulfuretted hydrogen colloidal sol can be generated in treatments of the sample process, make measurement result on the low side.Described molten sample acid is: the reagent of employing is red fuming nitric acid (RFNA) and perchloric acid, and the consumption of red fuming nitric acid (RFNA) and perchloric acid is respectively 20mL, 10mL; Take four parts, 0.2000g extreme pressure cutting fluid sample in 4 250mL beakers in, add the acid of 10mL, 15mL, 20mL, 25mL red fuming nitric acid (RFNA) respectively, after adding perchloric acid 3mL, 5mL, 10ml, 15mL, hot digestion product on middle temperature electric furnace, emit perchloric acid cigarette 5min after carry sample digestion completely, sulfur oxide generates sulfate radical.Very fast and the digestion of treatments of the sample completely for add red fuming nitric acid (RFNA) acid for 20mL, 25mL and perchloric acid be two samples of 10mL, 15mL, when ICP peristaltic pump promotes sample solution, acid in sample liquid can affect the atomizing effect of sample introduction speed and atomizer, and the addition selecting red fuming nitric acid (RFNA) acid is 20mL, perchloric acid addition is 10mL;
1.2ICP radio-frequency generator RF power is determined: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, be settled to 100mL scale, shake up with water, measures the light intensity value of sulphur; Regulate different RF watt levels to test, the increase of RF power makes line strength strengthen, but background increase simultaneously is faster, and therefore signal-to-background ratio increases with RF power and declines.Test display RF power is conducive to obtaining large signal-to-background ratio and Detection capability time low, but matrix effect is heavier; RF adopts high-powerly can alleviate matrix effect, but signal-to-background ratio and detection limit impaired, and easily burn out quarter bend when RF power is excessive.Test selects RF power to be 1.1KW;
1.3ICP is gases used is high-purity argon gas, the determination of argon flow amount: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, 100mL scale is settled to water, shake up, measure the light intensity value of sulphur, regulate plasma (orifice) gas, cold gas and assisted gas flow, measure the light intensity value of sulphur.Test selected plasma gas flow rate 38L/min, cold gas 20L/min and assisted gas flow 0.5L/min;
The determination of 1.4 quarter bend pipe core distances: get 2mL sulphur standard solution and be placed in a 100mL volumetric flask, add 1+1 perchloric acid 5mL, be settled to 100mL scale, shake up with water, measures the light intensity value of sulphur.Regulate the diverse location of quarter bend, measure the light intensity value of sulphur, torch tube hub pipe suitably should be increased to about 5.0mm place with the distance on edge under coil, and the absorbance of mensuration sulphur is maximum.Test determines that quarter bend pipe core distance is for 5.0mm;
The selection of 1.5 analysis spectral line wavelength: because the analysis spectral line of the sulphur of instrument recommendation is: 180.731nm, 182.624nm and 182.034nm, belong to ultraviolet spectral line, more suitable to sulfur content in extreme pressure cutting fluid, but in extreme pressure cutting fluid except sulfur-containing additive, also may there is phosphorous and adjuvant that is boracic, the analysis spectral line of phosphorus and boron is all positioned at ultraviolet region substantially, may cause interference to the analysis spectral line of sulphur, the recommendation spectral line of phosphorus has: 213.618nm, 178.283nm, 253.561nm, 214.914nm; The recommendation spectral line of boron has: 249.677nm, 208.956nm, 208.890nm, 182.641nm, 249.772nm; By carrying out length scanning to the mixed sample containing phosphorus, boron and sulphur, only have the 182.624nm of the 182.641nm convection current of boron to have spectral line interference, test selects 180.731nm to be the analysis spectral line of sulphur;
The elimination of 1.6 Matrix effects, due in extreme pressure cutting fluid except there is extreme-pressure additive, also other adjuvant various can be contained, in order to working sample and typical curve match, not sulfur-bearing cutting fluid bottoming is selected in test, add the sulphur mark liquid of corresponding different content, be mixed with standard working curve, in order to eliminate the interference that matrix brings;
2, analyzing detecting method:
2.1 samples clear up process: take cutting fluid 0.2000g in 250mL beaker in, add red fuming nitric acid (RFNA) 20mL, perchloric acid 10mL, sample is placed on 100-200 ° of hot digestion on middle temperature electric furnace, after treatments of the sample is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
The preparation of 2.4 working curves: the cutting fluid 0.2000g6 part taking not content is placed in the beaker of 6 250mL respectively, by the condition process of (2.1) Specimen eliminating, after cooling, proceeds in the volumetric flask of 6 100mL.Draw the sulphur standard solution that reagent is 1.0mg/mL: 0.0,1.0,2.0,4.0,6.0,8.0mL is placed in the volumetric flask of these 6 100mL aforementioned respectively, and being equivalent to sulfur content is 0.0,1.0,2.0,6.0,8.0mg/100mL.Be diluted with water to 100mL to carve, shake up, this group liquid is working curve liquid to be determined;
The determination of 2.5ICP inductive coupling plasma emission spectrograph condition of work:
ICP inductive coupling plasma emission spectrograph condition of work and running parameter are as following table:
2.6 sample tests: under selected instrument condition of work, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur to be determined, instrument is according to sulfur content and the corresponding luminous intensity values drawing curve measuring sulphur, the regression equation C=-1.21x+0.01 of curve, correlation coefficient r=0.99988.With working curve with sulfur content in condition working sample;
3, determination of recovery rates:
Take not sulphurous water base cutting fluid 0.2000g each 3 parts in 3 250mL beakers, add reagent 1mg/mL sulphur mark liquid respectively, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution in analyzing detecting method, measurement result is as shown in the table:
In table, the recovery of measurement result illustrates that the method accuracy of measurement is higher, meets the requirement that in extreme pressure water-base cutting fluid, sulfur content detects;
Take not sulfur-bearing cutting oil 0.2000g each 3 parts in 3 250mL beakers, add reagent 1mg/mL sulphur mark liquid respectively, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution in analyzing detecting method, measurement result is as shown in the table:
In table, the recovery of measurement result illustrates that the method accuracy of measurement is higher, meets the requirement that in extreme pressure cutting oil, sulfur content detects.
Reagent is: red fuming nitric acid (RFNA); Perchloric acid; Not sulfur-bearing cutting fluid; Not sulfur-bearing cutting oil; Sulphur standard solution:
1.0mg/mL; Phosphorus standard solution: 1.0mg/mL; Boron standard solution: 1.0mg/mL.It is pure that described reagent is analysis: water used is distilled water;
It is ICP inductive coupling plasma emission spectrograph with instrument;
Embodiment one
The impact of analyzing detecting method-Specimen eliminating acid consumption; Add perchloric acid 5mL:
2.1 samples clear up process: take extreme pressure cutting fluid 0.2000g in 250mL beaker in, add red fuming nitric acid (RFNA) 20mL, perchloric acid 5mL, sample is placed on hot digestion on middle temperature electric furnace, after treatments of the sample is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
The preparation of 2.4 working curves: the cutting fluid 0.2000g6 part taking not content is placed in the beaker of 6 250mL respectively, by the condition process of (2.1) Specimen eliminating, after cooling, proceeds in the volumetric flask of 6 100mL.Draw the sulphur standard solution that reagent is 1.0mg/mL: 0.0,1.0,2.0,4.0,6.0,8.0mL is placed in the volumetric flask of these 6 100mL aforementioned respectively, and being equivalent to sulfur content is 0.0,1.0,2.0,4.0,6.0,8.0mg/100mL.Be diluted with water to 100mL to carve, shake up, this liquid is working curve liquid to be determined;
2.5ICP inductive coupling plasma emission spectrograph condition of work:
ICP inductive coupling plasma emission spectrograph condition of work and running parameter are as following table:
2.6 sample tests: under selected instrument condition of work, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur to be determined, instrument is according to sulfur content and the corresponding luminous intensity values drawing curve measuring sulphur.Be 2.53% with working curve with sulfur content in condition working sample;
Embodiment two
Analysis determining method-perchloric acid 10mL,
1 sample clear up process: take extreme pressure cutting fluid 0.2000g in 250mL beaker in, add red fuming nitric acid (RFNA) 20mL, perchloric acid 10mL, sample is placed on hot digestion on middle temperature electric furnace, after treatments of the sample is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
Working curve preparation, ICP inductive coupling plasma emission spectrograph condition of work are with the step 2,3 of embodiment 1;
Sample tests: under selected instrument condition of work, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur to be determined, instrument is according to sulfur content and the corresponding luminous intensity values drawing curve measuring sulphur.Be 2.75% with working curve with sulfur content in condition working sample; .
Embodiment three
Analysis determining method-molten sample acid 15mL,
1 sample clear up process: take extreme pressure cutting fluid 0.2000g in 250mL beaker in, add red fuming nitric acid (RFNA) 20mL, perchloric acid 15mL, sample is placed on hot digestion on middle temperature electric furnace, after treatments of the sample is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
Working curve preparation, ICP inductive coupling plasma emission spectrograph condition of work are with the step 2,3 of embodiment 1;
Sample tests: under selected instrument condition of work, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur to be determined, instrument is according to sulfur content and the corresponding luminous intensity values drawing curve measuring sulphur.Be 2.80% with working curve with sulfur content in condition working sample.
Embodiment four
Analysis determining method, the reappearance to the mensuration of sulfur content in extreme pressure cutting fluid:
The digestion of sample: with the step 1 of embodiment 1;
Working curve preparation, ICP inductive coupling plasma emission spectrograph condition of work are with the step 2,3 of embodiment 1;
Sample tests: under the instrument condition of work selected, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminance value of working curve molten sulfur to be determined, according to sulfur content and the corresponding luminance value drawing curve measuring sulphur.The sulfur content of the luminance value and correspondence that measure sample solution sulphur to be determined is as following table:
By the operation of this instance analysis assay method step, carry out 7 replications, measurement result is as following table:
It is as shown in the table, and measurement result relatively, illustrates the assay method of sulfur content in extreme pressure cutting fluid of the present invention, and namely in ICP inductively coupled plasma emission spectrography mensuration extreme pressure cutting fluid, sulfur content has the advantage of structure favorable reproducibility.
Therefore, by the checking of above-mentioned embodiment, can find out that the method for sulfur content in ICP inductively coupled plasma emission spectrography of the present invention mensuration extreme pressure cutting fluid has precision high, favorable reproducibility, the advantages such as measurement result is accurate.
Claims (7)
1. the assay method of sulfur content in an extreme pressure cutting fluid, it is characterized in that: adopt red fuming nitric acid (RFNA) and perchloric acid, make sample catapepsis, be converted into inorganic samples aqueous solution, under inductive coupling plasma emission spectrograph ICP condition of work, measure sulfur content in cutting fluid; Specifically comprise that experiment condition is determined, analyzing detecting method, determination of recovery rates, its step is as follows:
1), experiment condition determines, comprising:
A. reagent is: the reagent of treatments of the sample, not sulfur-bearing cut reagent, standard solution; Wherein the reagent of treatments of the sample adopts red fuming nitric acid (RFNA), perchloric acid, and the consumption of red fuming nitric acid (RFNA) and perchloric acid is respectively 20 mL, 10mL; Standard solution is: sulphur standard solution: 1.0mg/mL, phosphorus standard solution: 1.0mg/mL, boron standard solution: 1.0mg/mL; Sulfur-bearing does not cut reagent is not sulfur-bearing cutting fluid, not sulfur-bearing cutting oil;
B. inductive coupling plasma emission spectrograph ICP measures the condition of work of sulfur content: comprising: the setting that plasma emission power, peristaltic pump sample lifting capacity, analysis spectral line selection, cold gas, assisted gas, plasma (orifice) gas, quarter bend pipe core distance, integral time are selected;
2), analyzing detecting method:
A. sample clear up process: take cutting fluid 0.2000g in 250mL beaker, add red fuming nitric acid (RFNA) 20mL, perchloric acid 10mL, cutting fluid sample is placed on hot digestion on middle temperature electric furnace, after liquid treatments of the sample to be cut is complete, continue heating and emit perchloric acid cigarette, make the sulphur complete oxidation in sample, be present in liquid to be determined with the form of sulfate radical;
B. prepare working curve: the cutting fluid 0.2000g6 part taking not sulfur-bearing is placed in the beaker of 6 250mL respectively, by the condition process of a step Specimen eliminating of step 2, after cooling, proceed in the volumetric flask of 6 100mL; The sulphur standard solution being 1.0mg/mL by absorption reagent is placed in the volumetric flask of aforesaid 6 100mL respectively, is diluted with water to 100mL scale, shakes up, and this group liquid is working curve liquid to be determined;
C. determine that the condition of work of inductive coupling plasma emission spectrograph ICP is: radio-frequency generator RF power: 1.1KW; Cooling gas flow: 20mL/min, assisted gas flow 0.5 mL/min, plasma gas flow rate 38 mL/min; Integral time 30s; Peristaltic pump sample lifting capacity 1.8mL, quarter bend pipe core distance is 5.0mm, analysis spectral line: 180.731nm;
d. sample tests: under the instrument condition of work determined, with the first point (0.0) suppressed zero in working curve liquid to be determined, measure the luminous intensity of working curve molten sulfur element to be determined, ICP inductive coupling plasma emission spectrograph is according to sulfur content and the corresponding luminous intensity values drawing curve measured, the regression equation C=-1.21x+0.01 of curve, correlation coefficient r=0.99988; Sulfur content in cutting fluid sample is measured with condition with working curve;
3), checking, determination of recovery rates is carried out to not sulfur-bearing cutting fluid, not sulfur-bearing cutting oil:
A. to not sulfur-bearing cutting fluid determination of recovery rates: take not sulfur-bearing cutting fluid 0.2000g each 3 parts in 3 250mL beakers, adding reagent is more respectively 1mg/mL sulphur standard solution, sulphur standard solution amount is 2.0mg, 4.0mg, 6.0mg, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution element sulphur in analyzing detecting method, measured value is respectively: 1.98mg, 4.01mg, 5.97mg, the recovery is respectively: 99.0%, 100.25%, 99.5%, meets the requirement that in extreme pressure cutting fluid, sulfur content detects;
B. to not sulfur-bearing cutting oil determination of recovery rates: take not sulfur-bearing cutting oil 0.2000g each 3 parts in 3 250mL beakers, to add reagent be respectively 1mg/mL sulphur standard solution amount is 2.0mg, 4.0mg, 6.0mg, by luminous intensity and the corresponding sulfur content of the operation steps working sample solution element sulphur in analyzing detecting method, measured value is respectively: 1.96mg, 4.00mg, 5.98mg, the recovery is respectively: 98.0%, 100.0%, 99.7%, meets the requirement that in extreme pressure cutting oil, sulfur content detects.
2. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, is characterized in that: the molten sample acid of treatments of the sample acid is: red fuming nitric acid (RFNA) and perchloric acid, and the consumption of red fuming nitric acid (RFNA) and perchloric acid is respectively 20 mL, 10mL; Take four parts, 0.2000g extreme pressure cutting fluid sample in 4 250mL beakers, add 10mL, 15 mL, 20 mL, 25 mL red fuming nitric acid (RFNA)s successively respectively, after adding perchloric acid 3 mL, 5mL, 10ml, 15mL successively respectively, hot digestion sample on middle temperature electric furnace, after treatments of the sample is complete, emit perchloric acid cigarette 5min, sulfur oxide generates sulfate radical;
And two samples of clear up that be addition be completely red fuming nitric acid (RFNA) to be 20 mL, 25mL and perchloric acid be 10mL, 15mL, when ICP peristaltic pump promotes sample solution, the addition adopting red fuming nitric acid (RFNA) is 20 mL, perchloric acid addition is 10mL.
3. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, it is characterized in that: the setting of described radio-frequency generator RF power: get 2mL sulphur standard solution and be placed in 100 mL volumetric flasks, add 1+1 perchloric acid 5mL, 100mL scale is settled to water, shake up, measure the luminous intensity values of sulphur; Regulate different radio-frequency generator RF watt levels to test, the increase of radio-frequency generator RF power makes line strength strengthen, and test display radio-frequency generator RF power is 1.1KW.
4. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, it is characterized in that: the argon gas flow of described ICP high-purity argon gas used is determined: get 2 mL sulphur standard solution and be placed in 100 mL volumetric flasks, add 1+1 perchloric acid 5mL, 100mL scale is settled to water, shake up, measure the light intensity value of sulphur, regulate plasma (orifice) gas, cold gas and assisted gas flow, measure the light intensity value of sulphur; Test selected plasma gas flow rate 38L/min, cold gas 20 L/min and secondary air 0.5L/min.
5. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, it is characterized in that: the determination of described quarter bend pipe core distance: get 2 mL sulphur standard solution and be placed in 100 mL volumetric flasks, add 1+1 perchloric acid 5mL, 100mL scale is settled to water, shake up, measure the light intensity value of sulphur; Regulate the diverse location of quarter bend, measure the light intensity value of sulphur, torch tube hub pipe should be increased to 5.0mm place with the distance on edge under coil, and the absorbance of mensuration sulphur is maximum; Test determines that quarter bend pipe core distance is for 5.0mm.
6. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, is characterized in that: the selection of described analysis spectral line wavelength:
The analysis spectral line of the sulphur that instrument is recommended is: 180.731nm, 182.624nm and 182.034nm, belong to ultraviolet spectral line, more suitable to sulfur content in extreme pressure cutting fluid or cutting oil,
In extreme pressure cutting fluid or extreme pressure cutting oil except sulfur-containing additive, also has adjuvant that is phosphorous and boracic, the analysis spectral line of phosphorus and boron is all positioned at ultraviolet region substantially, and the employing spectral line of phosphorus has: 213.618 nm, 178.283 nm, 253.561 nm, 214.914 nm; The employing spectral line of boron has: 249.677 nm, 208.956 nm, 208.890 nm, 182.641 nm, 249.772 nm; By carrying out length scanning to the mixed sample containing phosphorus, boron and sulphur, test selects 180.731nm to be the analysis spectral line of sulphur.
7. the assay method of sulfur content in a kind of extreme pressure cutting fluid according to claim 1, it is characterized in that: the selection of described analysis spectral line wavelength is used for the elimination of Matrix effects, in extreme pressure cutting fluid except having extreme-pressure additive, also other adjuvant various can be contained, in order to working sample and typical curve match, not sulfur-bearing cutting fluid bottoming is selected in test, adds corresponding sulphur standard solution, be mixed with standard working curve, in order to eliminate the interference that matrix brings.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008203032A (en) * | 2007-02-19 | 2008-09-04 | Japan Energy Corp | Analysis method of trace of metal |
| CN102998274A (en) * | 2012-11-30 | 2013-03-27 | 华南理工大学 | Method for rapidly measuring total sulfur content in black pulping liquor |
| CN103048312A (en) * | 2012-12-18 | 2013-04-17 | 浙江经济职业技术学院 | Hydraulic power steering system oil detection method based on atomic emission spectrometry |
-
2013
- 2013-05-31 CN CN201310215395.2A patent/CN103323447B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008203032A (en) * | 2007-02-19 | 2008-09-04 | Japan Energy Corp | Analysis method of trace of metal |
| CN102998274A (en) * | 2012-11-30 | 2013-03-27 | 华南理工大学 | Method for rapidly measuring total sulfur content in black pulping liquor |
| CN103048312A (en) * | 2012-12-18 | 2013-04-17 | 浙江经济职业技术学院 | Hydraulic power steering system oil detection method based on atomic emission spectrometry |
Non-Patent Citations (3)
| Title |
|---|
| ICP-AES有机进样测定润滑油中的S元素;李绍松等;《润滑油》;20061005;第21卷(第05期);62-64 * |
| 电感耦合等离子体光谱法测定硅烷偶联剂中硫含量;魏丰华等;《山东科学》;20031015;第16卷(第03期);55-58 * |
| 电感耦合等离子体发射光谱法测定植物中硫含量;蒋天成;《化学分析计量》;20070320;第16卷(第02期);51-52 * |
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